Petroleum Refining

Lecture 4
Treating Process
Catalytic hydrotreating is a hydrogenation process used to
remove about 90% of contaminants such as nitrogen, sulfur,
oxygen, and metals from liquid petroleum fractions. These
contaminants, if not removed from the petroleum fractions as
they travel through the refinery processing units, can have
detrimental effects on the equipment, the catalysts, and the
quality of the finished product. Typically, hydrotreating is done
prior to processes such as catalytic reforming so that the
catalyst is not contaminated by untreated feedstock.
Hydrotreating is also used prior to catalytic cracking to
reduce sulfur and improve product yields, and to upgrade
middle-distillate petroleum fractions into finished kerosene,
diesel fuel, and heating fuel oils. In addition . Hydrotreating
for sulfur removal is called hydrodesulfurization. In a
typical catalytic hydrodesulfurization unit, the feedstock
mixed with hydrogen, preheated in a fired heater (600-
800 F) and then charged under pressure (up to 1,000 psi)
through a fixed-bed catalytic reactor (Figure )
ammonia
(NH3). The reaction products leave the reactor and after
cooling to a low temperature enter a liquid/gas separator. The
hydrogen-rich gas from the high-pressure separation is
recycled to combine with the feedstock, and the low-pressure
gas stream rich in H2S is sent to a gas treating unit where
H2S is removed. The clean gas is then suitable as fuel for the
refinery furnaces. The liquid stream is the product from
hydrotreating and is normally sent to a stripping column for
removal of H2S and other undesirable components. In cases
where steam is used for stripping, the product is sent to a
Conversion Processes
1- Cracking

Cracking is a petroleum refining process in which heavy-molecular

weight hydrocarbons are broken up into light hydrocarbon

molecules by the application of heat and pressure, with or without
the use of catalysts, to derive a variety of fuel products. Cracking is
one of the principal ways in which crude oil is converted into useful
fuels such as motor gasoline, jet fuel, and home heating oil.
A. Thermal Cracking
Thermal cracking is a refining process in which heat (~800C)
and pressure (~700kPa) are used to break down, rearrange, or
combine hydrocarbon molecules. The first thermal cracking
process was developed around 1913. Distillate fuels and heavy
oils were heated under pressure in large drums until they
cracked into smaller molecules . However, this method
produced large amounts of solid, unwanted coke. This early
process has evolved into the following applications of thermal
cracking: visbreaking, steam cracking, and coking.
a) Steam Cracking Process
Steam cracking is a petrochemical process sometimes used
in refineries to produce olefinic raw materials (e.g., ethylene)
from various feedstock for petrochemicals manufacture. The
feedstock range from ethane to vacuum gas oil, with heavier
feeds giving higher yields of by-products such as naphtha.
The most common feeds are ethane, butane, and naphtha.
Steam cracking is carried out at temperatures of 1,500-
1,600 F, and at pressures slightly above atmospheric.
Naphtha produced from steam cracking contains benzene.
Residual from steam cracking is sometimes blended into
b) Visbreaking Process
Visbreaking, a mild form of thermal cracking, significantly lowers
the

viscosity of heavy crude-oil residue without affecting the boiling

point

range. Residual from the atmospheric distillation tower is heated

(800- 950 F) at atmospheric pressure and mildly cracked in a
heater (Figure1). It is then quenched with cool gas oil to control
overcracking, and flashed in a distillation tower. Visbreaking is used
to reduce viscosity of residues used for blending with lighter fuel oils
(Figure2)
Middle distillates may also be produced, depending on product
demand. The thermally cracked residue tar, which
accumulates in the bottom of the fractionation tower, is
vacuum flashed in a stripper and the distillate recycled. There
are two types of visbreaker operations, coil and furnace
cracking and soaker cracking. Coil cracking (Figure 1) uses
higher furnace outlet temperatures [885930F (473500C)]
and reaction times from one to three minutes, while soaker
cracking (Figure 2)uses lower furnace outlet temperatures
[800830F (427443C)] and longer reaction times.
The product yields and properties are similar, but the
soaker operation with its lower furnace outlet
temperatures has the advantages of lower energy
consumption and longer run times before having to shut
down to remove coke from the furnace tubes. Run times
of 36 months are common for furnace visbreakers and
618 months for soaker visbreakers.
c) Coking Processes
Coking is a severe method of thermal cracking used to upgrade heavy

residuals into lighter products or distillates (Figure 3). Coking produces

straight-run gasoline and various middle-distillate fractions used as

catalytic cracking feedstock. The process so completely reduces the
residue is a form of carbon called "coke." The two most common
processes are delayed coking and continuous (contact or fluid) coking.
Three typical types of coke are obtained (sponge coke, honeycomb
coke, and needle coke) depending upon the reaction mechanism, time,
temperature, and the crude feedstock.
1) Delayed Coking
In delayed coking (Figure 3) the heated charge (typically residuum
from

atmospheric distillation towers) is transferred to large coke drums

which provide the long residence time needed to allow the
cracking reactions to proceed to completion. Initially the heavy
feedstock is fed to a furnace which heats the residuum to high
temperatures (900-950 F) at low pressures (25-30 psi) and is
designed and controlled to prevent premature coking in the heater
tubes (Figure 3).
The mixture is passed from the heater to one or more
coker drums where the hot material is held
approximately 24 hours (delayed) at pressures of 25-75
psi, until it cracks into lighter products. Vapors from the
drums are returned to a fractionator where gas, naphtha,
and gas oils are separated out. The heavier hydrocarbons
produced in the fractionator are recycled through the
furnace.
2) Continuous Coking
Continuous (contact or fluid) coking is a moving-bed process that
operates at temperatures higher than delayed coking. In continuous
coking, thermal cracking occurs by using heat transferred from hot,
recycled coke particles to feedstock in a radial mixer, called a reactor,
at a pressure of 50 psi. Gases and vapors are taken from the reactor,
quenched to stop any further reaction, and fractionated. The reacted
coke enters a surge drum and is lifted to a feeder and classifier where
the larger coke particles are removed as product. The remaining coke is
dropped into the preheater for recycling with feedstock. Coking occurs
both in the reactor and in the surge drum. The process is automatic in
that there is a continuous flow of coke and feedstock.